A crystalline porous organic-inorganic hybrid is a porous material prepared formed by a coordinate bond between at least one metal ion or metal ion cluster and at least one aromatic carboxylate as an organic ligand. When preparing a porous organic-inorganic hybrid as described above, the solvothermal synthetic method is generally used, but a hydrothermal synthetic method may be used as well in order to increase the hydrothermal stability. As representative porous organic-inorganic hybrids prepared by the above synthetic method, mention can be made of a porous organic-inorganic hybrids having the formula of Cr3O(H2O)2X[C6H3(CO2)3]2 (X=F− or OH−) and its hydrate, Fe3O(H2O)2X[C6H3(CO2)3]2 (X=F− or OH−) and its hydrate, Cr3O(H2O)2X[C6H4(CO2)2]3 (X=F− or OH−) and its hydrate, has been reported [Science, 23, 2040 (2005); Chemical Communications, 2820 (2007); Accounts of Chemical Research, 38, 217 (2005)].
Meanwhile, the coordinate bond between a Group IV metal ion such as Zr or Ti and an organic ligand such as an aromatic carboxylate has a feature that the chemical bonding force is stronger than that of the conventional coordinate bond between a Group III metal ion such as Fe, Cr, Al or the like and a carboxylate ligand. Thus, in recent, active researches on the properties and application of the above materials including Zr or Ti are now carried out [Korean Patent Laid-Open No. 2009-0009849 (corresponding to PCT/EP2007/053704); Korean Patent Laid-Open No. 2009-0033172 (corresponding to PCT/EP2007/053781); WO 2009/133366; WO 2010/0945889; J. Am. Chem. Soc., 130, 13850 (2008); J. Am. Chem. Soc., 131, 10857 (2009)]. In recent, Korean Patent Application No. 10-2009-0089102 (Korean Patent Laid-Open No. 10-2011-0031731) has described a microwave synthesis and solvothermal synthesis of a porous organic-inorganic hybrid containing a tetravalent metal ion using a non-aqueous solvent. Said Korean Patent Application No. 10-2009-0089102 has produced a porous organic-inorganic hybrid comprising tetravalent metal by the solvothermal synthesis method.